The First Structurally Characterized Nonorganometallic Titanium(III) Alkoxo-Bridged Dinuclear Complexes

The reaction of [Ti4(OMe)14Cl2] (1) with an excess of AlMe3 gave the cocrystallite [Ti2(μ-OMe)2(μ-Cl)Cl3(thf)3]·[Ti2(μ-OMe)3Cl3(thf)3] (2·3) species in a 1:1 ratio. Similar to 2, [Ti2(μ-OEt)2(μ-Cl)Cl3(thf)3] (4) was obtained in the reaction of an equimolar mixture of TiCl4 and Ti(OEt)4 with Al/AlMe3. The short distance [2.543(1)av Å in 2·3 and 2.599(1) Å in 4] between “Ti(+3)” atoms, their diamagnetism, and ELF analysis indicate the presence of a Ti−Ti bond.